CN107108462B - Material for organic electroluminescent device - Google Patents

Material for organic electroluminescent device Download PDF

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CN107108462B
CN107108462B CN201580062361.1A CN201580062361A CN107108462B CN 107108462 B CN107108462 B CN 107108462B CN 201580062361 A CN201580062361 A CN 201580062361A CN 107108462 B CN107108462 B CN 107108462B
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特雷莎·穆希卡-费尔瑙德
埃尔维拉·蒙特内格罗
约亨·普菲斯特
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Merck Patent GmbH
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Abstract

The present invention relates to compounds of formula (1) suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices comprising these compounds.

Description

Material for organic electroluminescent device
The present invention relates to materials for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices comprising these materials.
The structure of organic electroluminescent devices (OLEDs) using organic semiconductors as functional materials is described, for example, in US 4,539,507, US 5151629, EP 0676461 and WO 98/27136. The luminescent materials employed here are increasingly organometallic complexes which exhibit phosphorescence instead of fluorescence (m.a. baldo et al, appl.phys.lett. (applied physical bulletin) 1999,75, 4-6).
According to the prior art, hole-transporting materials used in hole-transporting layers or hole-injecting layers are in particular triarylamine derivatives which generally contain at least two triarylamino groups or at least one triarylamino group and at least one carbazole group. These compounds are generally derived from diarylamino-substituted triphenylamines (TPA type), diarylamino-substituted biphenyl derivatives (TAD type) or combinations of these base compounds. Spirobifluorene derivatives substituted, for example, by diarylamino groups are also commonly used (for example, according to EP 676461 or US 7,714,145). There is still a need for alternative materials that can be used in OLED devices to obtain devices with good properties in terms of efficiency, lifetime and operating voltage.
It is therefore an object of the present invention to provide compounds which are suitable for use as hole-transport materials in fluorescent or phosphorescent OLEDs, in particular phosphorescent OLEDs, for example in hole-transport or exciton-blocking layers or as matrix materials in the light-emitting layer.
It has now been found that specific compounds described in more detail below achieve this object and lead to very good properties in organic electroluminescent devices, in particular with regard to lifetime, efficiency and operating voltage. This applies to phosphorescent and fluorescent electroluminescent devices, in particular using the compounds according to the invention as hole-transport materials or as matrix materials. The materials generally have high thermal stability and can therefore be sublimated without decomposition and residues. The invention thus relates to these materials and electronic devices comprising compounds of this type.
The present invention therefore relates to compounds of formula (1) below:
Figure BDA0001296792420000021
where the following applies to the symbols and labels used:
Ar1、Ar2identical or different at each occurrence to an aromatic or heteroaromatic ring system having 5 to 60C aromatic ring atoms, which may also be substituted in each case by one or more radicals R5Substituted, Ar1And Ar2Here too, they can be linked to one another via the radicals E;
e is, identically or differently at each occurrence, a single bond, N (R)5)、O、S、C(R5)2、C(R5)2-C(R5)2、Si(R5)2Or B (R)5)；
R1、R2、R3、R4Selected, identically or differently at each occurrence, from D, F, Cl, Br, I, CN, Si (R)6)3，N(R6)2Straight-chain alkyl, alkoxy or thioalkyl radicals having 1 to 40C atoms or branched or cyclic alkyl, alkoxy or thioalkyl radicals having 3 to 40C atoms, which may each be substituted by one or more radicals R6Substitution, in which in each case one or more non-adjacent CH2The radical may be substituted by Si (R)6)2、C＝NR6、P(＝O)(R6)、SO、SO2、NR6O, S or CONR6And in which one or more H atoms may be replaced by D, F, Cl, Br or I, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6Substituted aryloxy or heteroaryloxy radical having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R6Substituted, or aralkyl or heteroaralkyl radicals having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6By substitution, in which two or more adjacent substituents R1Or R2Or R3Or R4May optionally form a mono-or polycyclic ring system, which may be substituted by one or more radicals R6Substitution;
r is selected, identically or differently on each occurrence, from D, F, Cl, Br, I, CN, Si (R)6)3Straight-chain alkyl, alkoxy or thioalkyl radicals having 1 to 40C atoms or branched or cyclic alkyl, alkoxy or thioalkyl radicals having 3 to 40C atoms, which may each be substituted by one or more radicals R6Substitution, in which in each case one or more non-adjacent CH2The radical may be substituted by Si (R)6)2、C＝NR6、P(＝O)(R6)、SO、SO2、NR6O, S or CONR6Instead of and in which one or more H atoms may beWith aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, substituted by D, F, Cl, Br or I6Substituted aryloxy or heteroaryloxy radical having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R6Substituted, or aralkyl or heteroaralkyl radicals having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6Substituted, wherein two or more adjacent substituents R may optionally form a mono-or polycyclic ring system, which may be substituted by one or more radicals R6Substitution;
R5is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, CN, Si (R)6)3，N(R6)2Straight-chain alkyl, alkoxy or thioalkyl radicals having 1 to 40C atoms or branched or cyclic alkyl, alkoxy or thioalkyl radicals having 3 to 40C atoms, which may each be substituted by one or more radicals R6Substitution, in which in each case one or more non-adjacent CH2The radical may be substituted by Si (R)6)2、C＝NR6、P(＝O)(R6)、SO、SO2、NR6O, S or CONR6And in which one or more H atoms may be replaced by D, F, Cl, Br or I, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6Substituted aryloxy or heteroaryloxy radical having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R6Substituted, or aralkyl or heteroaralkyl radicals having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6By substitution, in which two or more adjacent substituents R5May optionally form a mono-or polycyclic ring system, which may be substituted by one or more radicals R6Substitution;
R6selected from H, D, F, an aliphatic hydrocarbon radical having 1 to 20C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D or F, two or more of whichMore adjacent substituents R6May form a mono-or polycyclic ring system with each other;
m is 0, 1,2 or 3;
n is 0, 1,2,3 or 4;
p, q are, identically or differently, 0 or 1;
r, s are, identically or differently, 0, 1,2,3 or 4; wherein p + r is less than or equal to 4 and q + s is less than or equal to 4.
t is, identically or differently at each occurrence, 0, 1,2 or 3.
Aryl groups in the sense of the present invention mean simple aromatic rings, i.e. benzene; or a fused (condensed) aryl group, such as naphthalene or phenanthrene. In contrast, aromatic groups, such as biphenyl or fluorene, which are connected to one another by single bonds, are not referred to as aryl groups, but rather as aromatic ring systems.
Heteroaryl groups in the sense of the present invention comprise at least one heteroatom in the aromatic ring, preferably a heteroatom selected from N, O and S. The heteroaryl group may contain only simple heteroaromatic rings, such as pyridine, triazine or thiophene, or it may be a fused (condensed) heteroaryl group, such as quinoline or carbazole.
An aromatic ring system in the sense of the present invention contains 6 to 60C atoms in the ring system, wherein the aromatic ring system can be built up, for example, from benzene, naphthalene, phenanthrene, fluorene and spirobifluorene or a combination of these groups. An aromatic ring system in the sense of the present invention is also intended in particular to mean a system in which a plurality of aryl radicals are additionally linked to one another directly or via carbon atoms. Thus, for example, in particular systems such as biphenyl, terphenyl, quaterphenyl, fluorene, 9' -spirobifluorene, 9-diarylfluorene, etc., are also intended to belong to aromatic ring systems in the sense of the present invention. An aromatic ring system as defined herein does not contain an amino group. Triarylamino groups are therefore not encompassed by the definition of aromatic ring systems.
Similar definitions apply to the term heteroaromatic ring system, which is considered to be a combination of two or more interconnected aryl or heteroaryl groups, at least one of which is a heteroaryl group.
An aralkyl group is considered to be an alkyl group substituted with an aryl group, wherein the aryl group is as defined above, andthe alkyl group may have 1 to 20C atoms and may be substituted as defined above for the alkyl group, and may have one or more CH substituted as defined above for the alkyl group2A group. In the aralkyl group, the alkyl group is a group bonded to the rest of the compound. Similar definitions apply to the term heteroaralkyl group, except that a heteroaryl group is present rather than an aryl group.
Aromatic hydrocarbon
An oxy group is considered to be an aryl group in which the aryl group is bonded via a divalent (ether) oxygen atom. Similar definitions apply to the term heteroaryloxy group, except that a heteroaryl group is present instead of an aryl group.
For the purposes of the present invention, it may generally contain 1 to 40 or 1 to 20C atoms and in addition individually H atoms or CH2Aliphatic hydrocarbon groups or alkyl groups or alkenyl or alkynyl groups whose groups may be substituted by the above-mentioned groups preferably refer to the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.
Alkoxy having 1 to 40C atoms preferably means methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy or 2,2, 2-trifluoroethoxy.
Thioalkyl having 1 to 40C atoms means in particular methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2, 2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.
In general, the alkyl, alkoxy or thioalkyl groups according to the invention may be straight-chain, branched or cyclic, in which one or more non-adjacent CH' s2The groups may be replaced by the groups mentioned above; furthermore, one or more H atoms may also be replaced by D, F, Cl, Br, I, CN or NO2F, Cl or CN is preferred, F or CN is further preferred, CN is particularly preferred instead.
Preferably, the two amino groups on the diaminophenyl group are in the meta position to each other. It is particularly preferred that they are in meta position to each other and are bonded to the spirobifluorene.
In a preferred embodiment of the present invention, p + q is 0 or 1. The compounds according to the invention therefore preferably contain one or two diaminobenzene groups. It is particularly preferred that p + q is 0 and the compounds according to the invention contain one diaminobenzene group.
In a preferred embodiment of the present invention, the compound of formula (1) is selected from the compounds of the following formulae (2) to (9),
Figure BDA0001296792420000061
Figure BDA0001296792420000071
wherein the symbols and indices used have the meanings given above.
In a particularly preferred embodiment of the present invention, the compounds of formulae (2) to (9) are selected from the compounds of formulae (2a) to (9a) below,
Figure BDA0001296792420000081
Figure BDA0001296792420000091
wherein the symbols and indices used have the meanings given above.
Very particular preference is given to compounds of the formulae (2b) to (9 b):
Figure BDA0001296792420000101
Figure BDA0001296792420000111
wherein m, n, r and s are, identically or differently, 0 or 1 and the other symbols used have the meanings given above.
Very particular preference is furthermore given to compounds of the formulae (2c) to (9 c):
Figure BDA0001296792420000112
Figure BDA0001296792420000121
wherein m, n, r and s are, identically or differently, 0 or 1 and the other symbols used have the meanings given above.
In a particularly preferred embodiment of the invention, the compounds according to the invention contain only one diaminobenzene group. This therefore preferably relates to compounds of the formulae (2), (3), (4) and (5) or (2a), (3a), (4a) and (5a) or (2b), (3b), (4b) and (5b) or (2c), (3c), (4c) and (5 c).
In another preferred embodiment of the present invention, the diaminobenzene group is bonded at the 2-or 4-position of the spirobifluorene. This therefore preferably relates to compounds of the formulae (2) and (3) or (2a) and (3a) or (2b) and (3 b).
Very particular preference is given to compounds of the formula (2) or (2a) or (2b) or (2 c).
Group Ar1And Ar2At least one of which, identically or differently at each occurrence, is selected from the group consisting of phenyl, fluorenyl, spirobifluorenyl, biphenyl, terphenyl, quaterphenyl, carbazolyl, dibenzofuranyl and dibenzothiophenyl, each of which may be substituted by one or more radicals R5And (4) substitution.
Group Ar1And Ar2Identical or different on each occurrence here are preferably selected from the group consisting of phenyl, fluorenyl, spirobifluorenyl, biphenyl, terphenyl, quaterphenyl, carbazolyl, dibenzofuranyl and dibenzothiophenyl, each of which may be substituted by one or more radicals R5And (4) substitution.
Group Ar1And Ar2The radicals which are identical or different on each occurrence are very preferably selected from the following formulae (10) to (66),
Figure BDA0001296792420000131
Figure BDA0001296792420000141
Figure BDA0001296792420000151
Figure BDA0001296792420000161
Figure BDA0001296792420000171
wherein the dotted bonds indicate bonds to nitrogen and the groups may be substituted by one or more groups R5Substituted, but preferably unsubstituted.
R in the groups of formulae (20) to (23), (53) and (54)5Preferably identical or different, represents an alkyl group having 1 to 10C atoms, in particular a methyl group, or a phenyl group, which may be substituted by one or more radicals R6And (4) substitution.
Preferred radicals Ar1And Ar2Selected, identically or differently at each occurrence, from the abovementioned radicals of the formulae (10), (11), (12), (13), (20), (21), (22), (23), (32), (33), (34), (35), (36), (37), (38), (39), (40), (41), (42), (43), (44), (45), (46), (47), (48), (49), (50) and (51). All possible combinations of these groups are likewise possible here.
Ar is particularly preferred1And Ar2Are selected, identically or differently at each occurrence, from the radicals of formulae (10), (11), (13), (20), (36), (37), (38), (41), (46) and (51) mentioned above.
Further, R in the groups of formulae (28) to (31) and (40) to (43) and (55) to (58) and (63) to (66)5Preferably represents a phenyl group, an ortho-biphenyl group, an meta-biphenyl group, a para-biphenyl group, a terphenyl group, a 1-naphthyl group or a 2-naphthyl group, which may be substituted by one or more radicals R6And (4) substitution.
Ar1And Ar2Identical or different at each occurrence is preferably selected from the groups of formulae (10), (13) and (20), which may be substituted by one or more radicals R5And (4) substitution.
Group Ar1And Ar2At least one of these is particularly preferably a radical of the formula (10), (13) or (20).
Two groups Ar of the above-mentioned formulae (11) to (66) bonded to nitrogen1And Ar2May be combined with each other as desired.
In a preferred embodiment of the inventionIn the formula, the group Ar is selected1And Ar2Making them different from each other.
In a preferred embodiment of the invention, the group Ar is chosen1And Ar2Making them identical to each other.
If in the compounds of the formulae (1) and (2) to (9) or in the preferred embodiment the group Ar1And Ar2By the group E being linked to each other, then the group-NAr1Ar2Preferably a structure having one of the following formulae (67) to (74),
Figure BDA0001296792420000181
Figure BDA0001296792420000191
wherein the symbols used have the meanings given above and the dashed bonds indicate bonds to the spirobifluorene. These radicals may also be substituted by one or more radicals R5Substituted, but preferably unsubstituted.
R in the radicals of the formulae (68) and (72)5Preferably identical or different, represents an alkyl group having 1 to 10C atoms, in particular a methyl group, or a phenyl group, which may be substituted by one or more radicals R6And (4) substitution.
Furthermore, R in the radicals of the formulae (71) and (73)5Preferably represents a phenyl group which may be substituted by one or more radicals R6And (4) substitution.
In a preferred embodiment of the invention, R1To R4Selected, identically or differently on each occurrence, from F, CN, straight-chain alkyl or alkoxy groups having 1 to 10C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 10C atoms, each of which may be substituted by one or more radicals R6Substitution of one or more non-adjacent CH2A group which may be replaced by O and in which one or more H atoms may be replaced by F, and aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms per radicalIn each case by one or more radicals R6And (4) substitution.
In a particularly preferred embodiment of the invention, R1To R4Selected, identically or differently on each occurrence, from F, a straight-chain alkyl radical having 1 to 5C atoms, a branched or cyclic alkyl radical having 3 to 6C atoms, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R6And (4) substitution.
Most preferred is R1To R4Selected from F, N (R) the same or different6)2Phenyl, methyl and tert-butyl.
In another preferred embodiment of the invention, R is selected, identically or differently on each occurrence, from F, CN, a linear alkyl or alkoxy group having 1 to 10C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10C atoms, each of which may be substituted by one or more radicals R6Substitution of one or more non-adjacent CH2The radicals may be replaced by O and in which one or more H atoms may be replaced by F, and aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R6And (4) substitution.
In a particularly preferred embodiment of the invention, R is selected, identically or differently on each occurrence, from F, a straight-chain alkyl radical having 1 to 5C atoms, a branched or cyclic alkyl radical having 3 to 6C atoms, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be interrupted by one or more radicals R6And (4) substitution.
Most preferably, R is selected from F, phenyl, methyl and t-butyl.
In another preferred embodiment of the present invention, the bond to Ar1Or Ar2Group R of5Selected, identically or differently on each occurrence, from H, F, CN, a straight-chain alkyl radical having 1 to 10C atoms, a branched or cyclic alkyl radical having 3 to 10C atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be mono-or hetero-substitutedOne or more radicals R6And (4) substitution.
In a particularly preferred embodiment of the invention, the bond to Ar1Or Ar2Group R of5Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having 1 to 5C atoms, a branched or cyclic alkyl radical having 3 to 6C atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may each be substituted by one or more radicals R6And (4) substitution.
R1To R6It is preferred here that no fused aryl or heteroaryl groups are included in which more than two aromatic or heteroaromatic six-membered rings are directly fused to one another, i.e. for example no anthracene or pyrene groups are included. Radical R1To R6It is particularly preferred that absolutely no fused aryl or heteroaryl groups in which aromatic or heteroaromatic six-membered rings are fused directly to one another, i.e. for example also no naphthalene groups, are contained.
Furthermore, two substituents R in the 9-position of the fluorene may be preferred5Together form a cycloalkyl ring preferably having 3 to 8C atoms, particularly preferably having 5 or 6C atoms.
Likewise, two substituents R in the formulae (68) and (72)5Can form ring systems with one another and thus form spiro ring systems, for example cycloalkyl rings, preferably having 3 to 8C atoms, particularly preferably having 5 or 6C atoms.
For compounds processed by vacuum evaporation, the alkyl group preferably has not more than 4C atoms, particularly preferably not more than 1C atom. For compounds which are processed from solution, suitable compounds are also those which are substituted by straight-chain, branched or cyclic alkyl groups having up to 10C atoms or by oligoarylene groups, for example ortho-, meta-, para-or branched terphenyl or quaterphenyl groups.
Particular preference is given to compounds of the formulae (1) and (2) to (9) and (2a) to (9a) and (2b) to (9b) and (2c) to (9c), where the abovementioned preferred embodiments are present at the same time. The following compounds are therefore particularly preferred:
Ar1、Ar2identically or differently, a radical of one of the formulae (10) to (66);
or-NAr1Ar2Represents a group of one of formulae (67) to (74);
e is, identically or differently on each occurrence, a single bond or C (R)1)2、N(R1) O or S;
R1to R4Selected, identically or differently on each occurrence, from F, CN, straight-chain alkyl or alkoxy groups having 1 to 10C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 10C atoms, each of which may be substituted by one or more radicals R6Substitution of one or more non-adjacent CH2The radicals possibly being replaced by O and one or more H atoms possibly being replaced by F, aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms which may in each case be replaced by one or more radicals R6Substitution;
r is selected, identically or differently on each occurrence, from F, CN, a straight-chain alkyl or alkoxy radical having 1 to 10C atoms or a branched or cyclic alkyl or alkoxy radical having 3 to 10C atoms, each of which may be substituted by one or more radicals R6Substitution of one or more non-adjacent CH2The radicals may be replaced by O and in which one or more H atoms may be replaced by F, and aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R6The substitution is carried out by the following steps,
if the radical R is5Is bonded to Ar1Or Ar2Then R is5Selected from H, F, CN, N (R), the same or different at each occurrence6)2A linear alkyl radical having 1 to 10C atoms, a branched or cyclic alkyl radical having 3 to 10C atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may each be substituted by one or more radicals R6Substitution;
or R bonded to the carbon bridging group in formulae (20) to (23), (53), (54), (68) and (72)5Identical or different are alkyl radicals having 1 to 10C atoms, in particular methyl, or phenyl radicals, which may be substituted by one or more radicals R6Substitution;
or R bonded to the nitrogen bridging group in formulae (28) to (31), (40) to (43) or (55) to (58), (63) to (66), (71) and (73)5Is a phenyl group which may be substituted by one or more radicals R6Substitution;
R6selected, identically or differently on each occurrence, from H, a straight-chain alkyl group having 1 to 10C atoms or a branched or cyclic alkyl group having 3 to 10C atoms or an aromatic ring system having 5 to 24C atoms;
m is 0 or 1;
n is 0 or 1;
p + q is 0 or 1;
r is 0 or 1;
s is 0 or 1;
t is 0 or 1.
More preferably R in the compounds listed above1To R4Selected from H, F, N (R) the same or different6)2Phenyl, methyl and tert-butyl.
Still more preferably, in the compounds listed above, t is 0.
Examples of suitable compounds according to the invention are the compounds shown in the following table:
Figure BDA0001296792420000241
Figure BDA0001296792420000251
Figure BDA0001296792420000261
Figure BDA0001296792420000271
Figure BDA0001296792420000281
Figure BDA0001296792420000291
Figure BDA0001296792420000301
Figure BDA0001296792420000311
Figure BDA0001296792420000321
Figure BDA0001296792420000331
the compounds according to the invention can be prepared by synthetic procedures known to those skilled in the art, such as halogenation, Hartwig-Buchwald coupling and Suzuki coupling.
The synthesis of diaminobenzene-spirobifluorenes is shown in scheme 1, where two routes to diaminobenzene-spirobifluorenes are shown.
Scheme 1:
a) first path
Figure BDA0001296792420000341
b) Second path
Figure BDA0001296792420000342
As shown in scheme 1a, halodiaminophenyl groups were synthesized from the corresponding trihalophenyl groups (compound a) by introducing two diarylamino groups.
Alternatively, as shown in scheme 1B, compound B may be used1And B2Diarylamino groups are introduced sequentially to obtain a halodiaminobenzene compound having two different diarylamino groups.
Finally, spirobifluorene groups are introduced by a C-C Suzuki coupling reaction between the boronic ester derivative C and the halodiaminobenzene.
The compounds according to the invention described above, in particular those substituted by reactive leaving groups such as bromine, iodine, triflate, boronic acid or boronic ester, can be used as monomers for preparing corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out via a halogen function or a boronic acid function.
The present invention therefore furthermore relates to oligomers, polymers or dendrimers comprising one or more compounds of formula (1), wherein one or more of the bonds forming the polymer, oligomer or dendrimer may be located at R1To R5At any desired position in substituted formula (1). Linking of compounds according to formula (1), which are part of the side chain or part of the main chain of an oligomer or polymer. An oligomer in the sense of the present invention means a compound which is composed of at least three monomer units. A polymer in the sense of the present invention means a compound which is composed of at least 10 monomer units. The polymers, oligomers or dendrimers according to the invention may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers according to the invention may be linear, branched or dendritic. In structures that are linked in a linear fashion, the units of formula (1) may be linked to one another directly or may be linked to one another via a divalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom or via a divalent aromatic or heteroaromatic group. In branched and dendritic structures, three or more units of formula (1) may be linked, for example, via a trivalent or multivalent group, for example via a trivalent or multivalent aromatic or heteroaromatic group, to form a branched or dendritic oligomer or polymer. The same preferred modes described above for the compounds of formula (1) apply to oligomeric, dendritic polymersA macromolecule and a repeat unit of formula (1) in a polymer.
To prepare oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Suitable and preferred comonomers are selected from fluorenes (for example according to EP 842208 or WO 00/22026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 06/061181), p-phenylenes (for example according to WO 92/18552), carbazoles (for example according to WO 04/070772 or WO 04/113468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (for example according to WO 05/014689 or WO 2007/006383), cis-or trans-indenofluorenes (for example according to WO 04/041901 or WO 04/113412), ketones (for example according to WO 05/040302), phenanthrenes (for example according to WO 05/104264 or WO 07/017066) or also a plurality of such units. The polymers, oligomers and dendrimers usually also contain further units, such as luminescent (fluorescent or phosphorescent) units, for example vinyl triarylamines (e.g. according to WO 07/068325) or phosphorescent metal complexes (e.g. according to WO 06/003000) and/or charge transport units, especially those based on triarylamines.
The polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular a long lifetime, high efficiency and good color coordinates.
The polymers and oligomers according to the invention are generally prepared by polymerizing one or more types of monomers, at least one of which produces a repeating unit of formula (1) in the polymer. Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions to produce C-C or C-N linkages are as follows:
(A) polymerizing SUZUKI;
(B) YAMAMOTO polymerization;
(C) STILLE polymerization; and
(D) HARTWIG-BUCHWALD polymerization.
The manner in which the polymerization can be carried out by these methods and the manner in which the polymer can thus be isolated and purified from the reaction medium are known to the person skilled in the art and are described in detail in the literature, for example in WO 2003/048225, WO 2004/037887 and WO 2004/037887.
The invention therefore also relates to a process for preparing the polymers, oligomers and dendrimers according to the invention, which are characterized in that they are prepared by SUZUKI polymerization, YAMAMOTO polymerization, STILLE polymerization or HARTWIG-BUCHWALD polymerization. The dendrimers according to the invention can be prepared by or analogously to methods known to the person skilled in the art. Suitable methods are described in the literature, such as described in Frechet, Jean m.j.; hawker, Craig J., "high-chlorinated polyphenylenes and high-chlorinated polyesters: new soluble, three-dimensional, Reactive Polymers (Hyperbranched polyphenylenes and Hyperbranched polyesters: new soluble, three-dimensional, Reactive Polymers)", Reactive & Functional Polymers (Reactive & Functional Polymers) (1995),26(1-3), 127-36; janssen, h.m.; meijer, E.W. "The Synthesis and characterization of dendritic molecules", Materials Science and Technology (1999),20(Synthesis of Polymers), 403-; tomalia, Donald a., "dendron molecules", Scientific American (1995),272(5), 62-6; WO 02/067343A1 and WO 2005/026144A 1.
The compounds according to the invention are suitable for use in electronic devices. Electronic device here means a device comprising at least one layer, wherein the layer contains at least one organic compound. However, the component may also comprise inorganic materials here or may also comprise layers which are composed entirely of inorganic materials.
The invention therefore furthermore relates to the use of the compounds according to the invention in electronic devices, in particular in organic electroluminescent devices.
The invention furthermore relates to electronic devices comprising at least one compound according to the invention. The preferred embodiments described above are equally applicable to electronic devices.
The electronic device is preferably selected from the group consisting of organic electroluminescent devices (organic light emitting diodes, OLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), Organic Dye Sensitized Solar Cells (ODSSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon emitting devices (d.m. koller et al, Nature Photonics 2008,1-4), but is preferably an organic electroluminescent device (OLED), particularly preferably a phosphorescent OLED.
The organic electroluminescent device and the light-emitting electrochemical cell may be used in various applications, for example in monochromatic or polychromatic displays, in lighting applications or in medical and/or cosmetic applications, for example in phototherapy.
The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, they may also comprise further layers, for example, in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. Also, an intermediate layer having, for example, an exciton blocking function may be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not necessarily be present.
The organic electroluminescent device may here comprise one light-emitting layer or a plurality of light-emitting layers. If a plurality of light-emitting layers are present, it is preferred that these layers have a plurality of emission peaks between 380nm and 750nm in total, resulting in white light emission as a whole, i.e., a plurality of light-emitting compounds capable of fluorescence or phosphorescence are used in the light-emitting layer. Particular preference is given to systems having three light-emitting layers, wherein the three layers exhibit blue, green and orange or red emission (see, for example, WO 2005/011013 for basic structures). It is possible here for all the light-emitting layers to be fluorescent or for all the light-emitting layers to be phosphorescent or for one or more light-emitting layers to be fluorescent and one or more further layers to be phosphorescent.
The compounds according to the invention according to the embodiments indicated above can be used here in different layers depending on the exact structure. Preference is given to organic electroluminescent devices which comprise the compounds of the formula (1) or the preferred embodiments as hole-transport materials in hole-transport or hole-injection or exciton-blocking or electron-blocking layers or as matrix materials for fluorescent or phosphorescent emitters, in particular for phosphorescent emitters, in the light-emitting layer. The preferred embodiments indicated above are also suitable for the use of the materials in organic electronic devices.
In a preferred embodiment of the present invention, the compound of formula (1) or said preferred embodiment is used as a hole transporting or hole injecting material in a hole transporting or hole injecting layer. The light-emitting layer can be fluorescent or phosphorescent. A hole injection layer in the sense of the present invention is a layer directly adjacent to the anode. A hole transport layer in the sense of the present invention is a layer located between the hole injection layer and the light emitting layer.
In a further preferred embodiment of the present invention, the compound of formula (1) or the preferred embodiment is used in an exciton blocking layer. The exciton blocking layer refers to the layer directly adjacent to the light-emitting layer on the anode side.
The compounds of the formula (1) or the preferred embodiments described are particularly preferably used in hole transport or exciton blocking layers.
In one embodiment of the invention, the compounds of formula (1) or the preferred embodiments are used in hole transporting or injection layers in combination with layers comprising hexaazatriphenylene derivatives, in particular hexacyanohexanyltriphenylene (e.g. according to EP 1175470). Thus, for example, the following combinations are preferred: anode-hexaazatriphenylene derivative-hole transport layer, wherein the hole transport layer comprises one or more compounds of formula (1) or the preferred embodiments. In this structure, too, a plurality of successive hole transport layers can be used, at least one of which comprises at least one compound of the formula (1) or the preferred embodiment. Another preferred combination is as follows: anode-hole transport layer-hexaazatriphenylene derivative-hole transport layer, wherein at least one of the two hole transport layers comprises one or more compounds of formula (1) or the preferred embodiments. Instead of one hole transport layer, a plurality of successive hole transport layers can also be used in this structure, at least one hole transport layer containing at least one compound of the formula (1) or the preferred embodiments.
If the compound according to formula (1) is employed as hole-transporting material in a hole-transporting layer, hole-injecting layer, exciton-blocking layer or electron-blocking layer, the compound can be used as pure material, i.e. in a proportion of 100% in the layer, or it can be used in combination with one or more other materials. According to a preferred embodiment, in this case, the one or other compound used in combination with the compound according to formula (1) is a p-type dopant. The preferred p-type dopant to be used is an electron acceptor compound, preferably one that can oxidize one or more of the other compounds of the mixture.
The p-type dopant is preferably present in the layer comprising the compound according to the invention in a concentration of 0.1 to 20 vol.%, preferably 0.5 to 12 vol.%, more preferably 1 to 8 vol.% and most preferably 2 to 6 vol.%.
Particularly preferred p-type dopants for use in combination with the compounds according to the invention are the compounds disclosed in one or more of the following documents: WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009/003455, WO 2010/094378, WO 2011/120709, US 2010/0096600 and WO 2012/095143.
Highly preferred p-type dopants for use in devices according to the invention are quinodimethane, azaindenofluorenedione, azaphenalene, azatriphenylene, I2Metal halides, preferably transition metal halides, metal oxides, preferably transition metal oxides or metal oxides containing at least one metal of main group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd or Pt with ligands having at least one bound oxygen atom. Further preferred are transition metal oxides such as rhenium oxide, molybdenum oxide and tungsten oxide, more preferably Re2O7、MoO3、WO3And ReO3。
Preferred p-type dopants are furthermore the following compounds:
Figure BDA0001296792420000401
Figure BDA0001296792420000411
in a further preferred embodiment of the present invention, the compounds of the formula (1) or the preferred embodiments are used as matrix materials for fluorescent or phosphorescent compounds, in particular phosphorescent compounds, in the light-emitting layer. The organic electroluminescent component can comprise a light-emitting layer or a plurality of light-emitting layers, wherein at least one light-emitting layer comprises at least one compound according to the invention as a matrix material.
If the compound of the formula (1) or the preferred embodiment is used as a matrix material for light-emitting compounds in the light-emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the sense of the present invention refers to light emission from an excited state with spin multiplicities >1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes containing transition metals or lanthanides, in particular all luminescent iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.
The mixture comprising the compound of the formula (1) or the preferred embodiment and the luminescent compound comprises between 99.9% by weight and 1% by weight, preferably between 99% by weight and 10% by weight, particularly preferably between 97% by weight and 60% by weight, in particular between 95% by weight and 80% by weight, of the compound of the formula (1) or the preferred embodiment, based on the entire mixture comprising emitter and matrix material. Accordingly, the mixture comprises between 0.1% and 99% by weight, preferably between 1% and 90% by weight, particularly preferably between 3% and 40% by weight, in particular between 5% and 20% by weight, of luminophore, based on the entire mixture comprising luminophore and matrix material. The above-indicated definitions apply in particular if the layer is applied from solution. The same values apply if the layers are applied by vacuum evaporation, the percentages in this case being shown in% by volume in each case.
A particularly preferred embodiment of the present invention is the use of the compounds of the formula (1) or the preferred embodiment in combination with a further matrix material as matrix material for phosphorescent emitters. Particularly suitable matrix materials which can be employed in combination with the compounds of the formula (1) or the preferred embodiments are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, for example CBP (N, N-biscarbazolylbiphenyl), m-CBP or the carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851, indolocarbazole derivatives, for example according to 2007/063754 or WO 2008/056746, indenocarbazole derivatives, for example according to WO 2010/136109 and WO 2011/000455, azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, ambipolar matrix materials, for example according to WO 2007/137725, silanes, for example according to WO 005/111172, azaborol or boronates, for example according to WO 2006/117052, triazine derivatives, for example according to WO 2010/015306, WO 2007/063754 or WO 08/056746, zinc complexes, for example according to EP 652273 or WO 2009/062578, fluorene derivatives, for example according to WO 2009/124627, diazasisilacyclopentadiene or tetraaza-silacyclopentadiene derivatives, for example according to WO 2010/054729, diazapalkalene derivatives, for example according to WO 2010/054730, or bridged carbazole derivatives, for example according to US 2009/0136779, WO 2010/050778, WO 2011/042107 or WO 2011/088877. Furthermore, electron neutral co-hosts having neither hole nor electron transport properties as described, for example, in WO 2010/108579 may be used.
It is likewise possible to use two or more phosphorescent emitters in a mixture. In this case, the luminophores emitting at shorter wavelengths act as co-hosts in the mixture.
Suitable phosphorescent compounds (═ triplet emitters) are in particular compounds which, when excited appropriately, emit preferably in the visible region and additionally contain at least one atom having an atomic number of greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular metals having this atomic number. The phosphorescent emitters used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper.
Examples of such emitters are disclosed in the following applications: WO 2000/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO 2011/157339 or WO 2012/007086. In general, all phosphorescent complexes as used for phosphorescent OLEDs according to the prior art and as known to the person skilled in the art of organic electroluminescence are suitable, and the person skilled in the art will be able to use further phosphorescent complexes without inventive effort.
Examples of triplet emitters used in the devices according to the present application are shown in the table below.
Figure BDA0001296792420000431
Figure BDA0001296792420000441
Figure BDA0001296792420000451
Figure BDA0001296792420000461
Figure BDA0001296792420000471
Figure BDA0001296792420000481
Figure BDA0001296792420000491
In a further embodiment of the present invention, the organic electroluminescent device according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer is directly adjacent to the hole injection layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described in, for example, WO 2005/053051. Furthermore, metal complexes can be used which are identical or similar to the metal complexes in the light-emitting layer directly adjacent to the light-emitting layer as hole-transporting or hole-injecting material, as described, for example, in WO 2009/030981.
The compounds of the formula (1) or the preferred embodiments described above can furthermore be used in hole-transport layers or exciton-blocking layers or as a matrix in the light-emitting layer.
In the other layers of the organic electroluminescent device according to the invention, all materials as are generally used according to the prior art can be used. The person skilled in the art will thus be able to use all materials known for organic electroluminescent devices in combination with the compounds of the formula (1) or preferred embodiments according to the invention without inventive effort.
Preferred fluorescent emitter materials are selected from the class of arylamines. Arylamine or aromatic amine in the sense of the present invention means a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, particularly preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic pyrenesFamily of people
Figure BDA0001296792420000501
Amines or aromatics
Figure BDA0001296792420000502
A diamine. Aromatic anthracenamines are understood to mean compounds in which one diarylamino group is bonded directly to the anthracene group, preferably in the 9-position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are bonded directly to the anthracene group, preferably in the 9, 10-position. Aromatic pyrene amine, pyrene diamine,
Figure BDA0001296792420000503
Amines and
Figure BDA0001296792420000504
diamines are defined analogously thereto, wherein the diarylamino groups are bonded to the pyrene preferably in the 1-position or in the 1, 6-position. Further preferred luminophore materials are selected from indenofluorenylamines or indenofluorenylamines, for example according to WO 06/122630, benzindenofluorenylamines or benzindenofluorenyldiamines, for example according to WO 08/006449, and dibenzoindenofluorenylamines or dibenzoindenofluorenyldiamines, for example according to WO 07/140847. Examples of emitter materials from the styrylamine class are substituted or unsubstituted tristilbene amines or emitter materials described in WO 06/000388, WO 06/058737, WO 06/000389, WO 07/065549 and WO 07/115610. Preference is furthermore given to the fused hydrocarbons disclosed in application WO 10/012328.
The host material that can be preferably used for the fluorescent dopant is a material from various species. Preferred matrix materials are selected from oligoarylene species (e.g. 2,2',7,7' -tetraphenylspirobifluorene according to EP 676461, or dinaphthylanthracene), in particular oligoaryls containing fused aromatic groups, oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypentametal complexes (e.g. according to WO 2004/081017), hole-conducting compounds (e.g. according to WO 2004/058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (e.g. according to WO 2005/084081 and WO 2005/084082), atropisomers (e.g. according to WO 2006/048268), boronic acid derivatives (e.g. according to WO 2006/117052), or benzanthracenes (e.g. according to WO 2008/145239). Suitable matrix materials are furthermore preferably compounds according to the invention. Particularly preferred matrix materials, in addition to the compounds according to the invention, are selected from the following classes: oligoarylene, which includes naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, oligoarylene vinylene groups, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the group of oligomeric arylene groups, which comprise anthracene, benzanthracene, triphenylene and/or pyrene or atropisomers of these compounds. An oligoarylene in the sense of the present invention is intended to mean a compound in which at least three aryl or arylene groups are bonded to one another.
Suitable charge transport materials which can be used in addition to the compounds according to the invention in the hole injection or hole transport layer or in the electron transport layer of the organic electroluminescent device according to the invention are, for example, the compounds disclosed in y.shirota et al, chem.rev. (chemical review) 2007,107(4),953-1010 or other materials as employed in these layers according to the prior art.
Preference is furthermore given to organic electroluminescent devices, characterized in that one or more layers are applied by means of a sublimation process in which the material is present in a vacuum sublimation apparatus generally less than 10%-5Mbar, preferably less than 10-6Vapor deposition at an initial pressure of millibar. However, the initial pressure may also be even lower, e.g. less than 10-7Millibar.
Preference is likewise given to organic electroluminescent devices, characterized in that one or more layers are applied by means of the OVPD (organic vapor deposition) method or by means of carrier gas sublimation, the material being described at 10-5Applied at a pressure between mbar and 1 bar. A particular example of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly via a nozzle and is therefore structured (e.g., m.s. arnold et al, appl.phys. lett. (applied physical flash) 2008,92, 053301).
Preference is furthermore given to organic electroluminescent devices, characterized in that one or more layers are produced from solution, for example by spin coating or by means of any desired printing method, such as LITI (photo-induced thermal imaging, thermal transfer), inkjet printing, screen printing, flexographic printing, offset printing or nozzle printing. For this purpose, soluble compounds, for example obtained by suitable substitution, are required. These processes are also particularly suitable for the compounds according to the invention, since these generally have very good solubility in organic solvents.
Also possible are hybrid processes, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition. Thus, for example, the light-emitting layer may be applied from solution and the electron-transporting layer may be applied by vapor deposition.
These methods are generally known to the person skilled in the art and can be applied by him, without inventive effort, to organic electroluminescent devices comprising the compounds according to the invention.
For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds according to the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dioxane
Figure BDA0001296792420000521
Alkanes, phenoxytoluenes, especially 3-phenoxytoluene, (-) -fenchone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, α -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, Diethylene glycol dibutyl ether, triethylene glycol dimethyl ether and diethylene glycolAlcohol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or a mixture of these solvents.
The invention therefore furthermore relates to formulations, in particular solutions, dispersions or emulsions, comprising at least one compound of the formula (1) or at least one polymer, oligomer or dendrimer containing at least one unit of the formula (1) and at least one solvent, preferably an organic solvent. The ways in which this type of solution can be prepared are known to the person skilled in the art and are described, for example, in WO 2002/072714, WO 2003/019694 and the references cited therein.
The invention furthermore relates to mixtures comprising at least one compound of the formula (1) or the preferred embodiments indicated above and at least one further compound. If the compounds according to the invention are used as matrix materials, the further compounds may, for example, be fluorescent or phosphorescent dopants. The mixture may then also additionally comprise another material as an additional matrix material.
The present invention is explained in more detail by the following examples, without wishing to limit the present invention thereto. Based on the description, a person skilled in the art will be able to carry out the invention and prepare further compounds according to the invention throughout the scope of the disclosure without inventive effort and use them in electronic devices or use the method according to the invention.
Examples
A) Synthetic examples
Example (b):
unless otherwise indicated, the following syntheses were carried out under a protective atmosphere. Starting materials may be purchased from ALDRICH or ABCR. In the case of starting materials known from the literature, the numbers in brackets are the corresponding CAS numbers.
Example 1:
synthesis of Compound (1-1)
Figure BDA0001296792420000541
Intermediate (A-1): synthesis of N, N, N ', N' -Tetrabiphenyl-4-yl-5-chloro-benzene-1, 3-diamine
Tri-tert-butylphosphine (11.1mL of a 1.0M solution in toluene, 11.1mmol), palladium acetate (1.25g, 5.55mmol) and cesium carbonate (75.0g, 232mmol) were added to a solution of bis-biphenyl-4-yl-amine (CAS Nr.102113-98-4) (59.0g, 185mmol) and 1, 3-dibromo-5-chlorobenzene (25g, 92mol) in degassed toluene (600mL), and the mixture was heated at reflux for 2 hours. The reaction mixture was cooled to room temperature, expanded with toluene and filtered through celite. The filtrate was evaporated in vacuo and the residue was crystallized from heptane/toluene. Yield: 67.7g, 75%.
The following compounds were obtained analogously:
Figure BDA0001296792420000542
Figure BDA0001296792420000551
Figure BDA0001296792420000561
Figure BDA0001296792420000571
Figure BDA0001296792420000581
intermediate (B-1): synthesis of spirobifluorene-boronic acid ester derivatives
1a) Synthesis of 4-bromospiro-9, 9' -bifluorene
Figure BDA0001296792420000582
60g (188.5mmol) of 2,2-Dibromo-biphenyl (CAS 13029-09-9) was dissolved in 750mL dry THF and cooled to-78 ℃. 75.4mL (188.5mmol) of a 2.5M solution of nBuLi in heptane were added dropwise. After 1 hour, a solution of 34.6g of fluorenone (188.5mmol) (CAS 486-25-9) in 250mL THF was added dropwise. The reaction mixture was allowed to reach room temperature overnight, then saturated NH was used4The Cl (100mL) solution was quenched, the mixture was stirred briefly, the organic phase was separated, and the solvent was removed in vacuo. The residue is suspended at 40 ℃ in 500ml of glacial acetic acid, 0.5ml of concentrated hydrochloric acid is added to the suspension, and the mixture is then stirred for a further 2 hours at 100 ℃. After cooling, the precipitated solid is filtered off with suction, washed once with 100ml of glacial acetic acid, three times with 100ml of ethanol each time, and finally from two
Figure BDA0001296792420000583
And (4) recrystallizing the alkane. Yield: 70.1g (169mmol), 90%; according to1H NMR, purity about 98%.
The synthesis of additional brominated spirobifluorene derivatives was carried out analogously:
Figure BDA0001296792420000584
Figure BDA0001296792420000591
Figure BDA0001296792420000601
2a) synthesis of 4-bromospiro-9, 9' -bifluorene (B-1)
Figure BDA0001296792420000602
60g (152mmol) of 4-bromospiro-9, 9 '-bifluorene, 47.2g (182.1mmol) of bis-pinacolato diboron, 3.72g (4.55mmol) of 1,1' -bis (diphenylphosphino) -ferrocene-dichloropalladium (II) dichloromethane complex, 44.7(455mmol) of potassium acetate and 600ml of toluene were heated at reflux for 16 hours. After cooling, 200ml of water were added, the mixture was stirred for a further 30 minutes, the organic phase was separated off, it was filtered through a short bed of celite, and the solvent was subsequently removed in vacuo. The residue was recrystallized several times from heptane/toluene. Yield: 67.1g, 96%.
The synthesis of additional spirobifluoreneboronic acid ester derivatives was carried out analogously:
Figure BDA0001296792420000603
Figure BDA0001296792420000611
Figure BDA0001296792420000621
synthesis of Compound (1-1)
392mg (0.53mmol) of palladium dichloride-bis (tricyclohexylphosphine), 39. mu.L of hydrazine hydroxide (0.8mmol) and sodium metaborate (11g, 40mmol) are added to a solution of 20g (27mmol) of N, N, N ', N' -tetra-biphenyl-4-yl-5-chloro-benzene-1, 3-diamine (A-1) and 10g (28mmol) of 4-spirobifluorene-boronate (B1) in 430mL of THF, and the mixture is heated at reflux for 20 hours. The reaction mixture was cooled to room temperature, expanded with toluene and filtered through celite. The filtrate was expanded with water, re-extracted with toluene and the combined organic phases were dried and evaporated in vacuo. The residue was recrystallized from heptane/toluene and sublimed in vacuo. Compound (1-1) was obtained as a pale yellow solid (21.0g, 76% of theory).
The synthesis of compounds 1-2 to 1-29 was performed analogously. After recrystallization, the material is sublimed and tempered under high vacuum.
Figure BDA0001296792420000631
Figure BDA0001296792420000641
Figure BDA0001296792420000651
Figure BDA0001296792420000661
Figure BDA0001296792420000671
Figure BDA0001296792420000681
B) Device embodiments
The OLEDs according to the invention and the OLEDs according to the prior art are manufactured by the general method according to WO 2004/058911, which is adapted according to the conditions described here (change of layer thickness, material).
The substrate used was a glass plate coated with structured ITO (indium tin oxide) at a thickness of 50 nm. The OLEDs have in principle the following layer structure: substrate/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/Electron Blocking Layer (EBL)/emission layer (EML)/Electron Transport Layer (ETL)/Electron Injection Layer (EIL) and finally a cathode. The cathode is formed of an aluminum layer having a thickness of 100 nm. The exact structure of the OLED is indicated in the individual experiments described below. The structure of the material used to make the OLED is shown in table 1.
All materials were applied by thermal vapor deposition in a vacuum chamber. The light-emitting layer always consists of at least one host material (host material) and a light-emitting dopant (emitter), which is mixed with this host material or host materials in a specific volume ratio by coevaporation. For example, the expression H1: SEB (5%) means that the material H1 is present in a proportion of 95% by volume in the layer and SEB is present in a proportion of 5% in said layer. The layer composition (where only the percentage of the second material is given) adds up to 100% to the percentage of the first material. Similarly, the electron transport layer may also be composed of a mixture of two materials.
The OLEDs are characterized by standard methods. For this purpose, the external quantum efficiency (EQE, measured in percentages) is determined, which is calculated as a function of the luminous density from a current-voltage-luminous density characteristic line (IUL characteristic line) which exhibits lambertian emission characteristics, and the lifetime is determined. Expression EQE @10mA/cm2The indication is at 10mA/cm2External quantum efficiency at the operating luminous density of (a). LT80@60mA/cm2Is defined as being at 60mA/cm2The time at which the luminance of the OLED device drops to 80% of its initial luminous intensity at a constant driving current density. The data obtained for the various OLEDs are summarized in the text below.
Use of the compounds according to the invention as hole transport materials in fluorescent OLEDs
In particular, the compounds according to the invention are suitable as HIL, HTL or EBL in OLEDs. They are suitable as monolayers and also as mixed components for use as HILs, HTLs, EBLs or in EMLs. The samples comprising the compounds according to the invention showed high efficiency (tables 2 and 3) and high lifetime (table 3).
Figure BDA0001296792420000701
Example 1
Singlet blue devices (E1, E2, E3 and E4) were fabricated having the following structure:
Figure BDA0001296792420000702
Figure BDA0001296792420000711
additional singlet blue devices with structures E5 and E6 were fabricated:
Figure BDA0001296792420000712
all devices were at 10mA/cm2All exhibit an operating voltage of 3.9V-4.0V at the drive current density of (a).

Claims (18)

1. A compound of the following formula (1):
Figure FDA0002453363780000011
where the following applies to the symbols and labels used:
Ar1、Ar2identical or different at each occurrence to an aromatic or heteroaromatic ring system having 5 to 60C aromatic ring atoms, which may also be substituted in each case by one or more radicals R5Substitution;
R1、R2、R3、R4selected, identically or differently at each occurrence, from D, F, CN, Si (R)6)3，N(R6)2Straight-chain alkyl radicals having 1 to 40C atoms or branched or cyclic alkyl radicals having 3 to 40C atoms, each of which may be substituted by one or more radicals R6Substituted, or aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6Substitution;
r is selected, identically or differently on each occurrence, from D, F, CN, Si (R)6)3Straight-chain alkyl radicals having 1 to 40C atoms or branched or cyclic alkyl radicals having 3 to 40C atoms, each of which may be substituted by one or more radicals R6Substituted, or aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6Substitution;
R5selected, identically or differently at each occurrence, from H, D, F, CN, Si (R)6)3，N(R6)2Straight-chain alkyl radicals having 1 to 40C atoms or branched or cyclic alkyl radicals having 3 to 40C atoms, each of which may be substituted by one or more radicals R6Substituted, or aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R6Substitution;
R6selected from H, D, F, an aliphatic hydrocarbon radical having 1 to 20C atoms or an aromatic or heteroaromatic ring system having 5 to 30C atoms, wherein one or more H atoms may be replaced by D or F;
m is 0, 1,2 or 3;
n is 0, 1,2,3 or 4;
p and q are 0;
r, s are, identically or differently, 0, 1,2,3 or 4; wherein p + r is less than or equal to 4 and q + s is less than or equal to 4;
t is, identically or differently at each occurrence, 0, 1,2 or 3.
2. The compound according to claim 1, which is selected from the compounds of the following formulae (2) to (5),
Figure FDA0002453363780000021
Figure FDA0002453363780000031
wherein the symbols and indices used are as defined in claim 1.
3. The compound according to claim 1 or 2, selected from the compounds of the following formulae (2a) to (5a),
Figure FDA0002453363780000032
Figure FDA0002453363780000041
wherein the symbols and indices used are as defined in claim 1 or 2.
4. The compound according to claim 1 or 2, selected from the compounds of the following formulae (2b) to (5b),
Figure FDA0002453363780000042
Figure FDA0002453363780000051
wherein m, n, r and s are, identically or differently, 0 or 1;
and the other symbols used are as defined in claim 1 or 2.
5. The compound according to claim 1 or 2, selected from the compounds of the following formulae (2c) to (5c),
Figure FDA0002453363780000052
Figure FDA0002453363780000061
wherein m, n, r and s are, identically or differently, 0 or 1;
and the other symbols used are as defined in claim 1 or 2.
6. Compound according to claim 1 or 2, characterized in that the group Ar1And Ar2At least one of which, identically or differently at each occurrence, is selected from the group consisting of phenyl, fluorenyl, spirobifluorenyl, biphenyl, terphenyl, quaterphenylCarbazolyl, dibenzofuranyl and dibenzothiophenyl, each of which may be substituted by one or more radicals R5And (4) substitution.
7. Compound according to claim 1 or 2, characterized in that the group Ar1And Ar2At least one of which is selected, identically or differently on each occurrence, from the radicals of the following formulae (10) to (66),
Figure FDA0002453363780000062
Figure FDA0002453363780000071
Figure FDA0002453363780000081
Figure FDA0002453363780000091
Figure FDA0002453363780000101
wherein the dotted bonds indicate bonds to nitrogen and the groups may be substituted by one or more groups R5And (4) substitution.
8. The compound according to claim 1 or 2, characterized in that the groups Ar are selected identically1And Ar2。
9. The compound according to claim 1 or 2, characterized in that the group Ar is selected1And Ar2Making them different from each other.
10. Compound according to claim 1 or 2, characterized in that R1To R4Selected, identically or differently on each occurrence, from F, CN, a straight-chain alkyl radical having from 1 to 10C atoms or a branched or cyclic alkyl radical having from 3 to 10C atoms, each of which may be substituted by one or more radicals R6Substituted, or aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R6And (4) substitution.
11. The compound of claim 1 or 2, characterized by being bonded to Ar1Or Ar2Group R of5Selected from H, F, CN, N (R), the same or different at each occurrence6)2A linear alkyl radical having 1 to 10C atoms, a branched or cyclic alkyl radical having 3 to 10C atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may each be substituted by one or more radicals R6And (4) substitution.
12. The compound of claim 1 or 2, wherein:
Ar1、Ar2identically or differently, a radical of one of the formulae (10) to (66);
R1to R4Selected, identically or differently on each occurrence, from F, CN, straight-chain alkyl or alkoxy groups having 1 to 10C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 10C atoms, each of which may be substituted by one or more radicals R6Substituted, or aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R6Substitution;
r is selected, identically or differently on each occurrence, from F, CN, a straight-chain alkyl radical having 1 to 10C atoms or a branched or cyclic alkyl radical having 3 to 10C atoms, each of which may be substituted by one or more radicals R6Substituted, or aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms, which may in each case be substituted by one orPlural radicals R6The substitution is carried out by the following steps,
if the radical R is5Is bonded to Ar1Or Ar2Then R is5Selected from H, F, CN, N (R), the same or different at each occurrence6)2A linear alkyl radical having 1 to 10C atoms, a branched or cyclic alkyl radical having 3 to 10C atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may each be substituted by one or more radicals R6Substitution;
or R bonded to the carbon bridging group in formulae (20) to (23), (53) and (54)5Identical or different are alkyl groups or phenyl groups having 1 to 10C atoms, which may be substituted by one or more radicals R6Substitution;
or R bonded to the nitrogen bridging group in formulae (28) to (31), (40) to (43) or (55) to (58) and (63) to (66)5Is a phenyl group which may be substituted by one or more radicals R6Substitution;
R6selected, identically or differently on each occurrence, from H, a straight-chain alkyl group having 1 to 10C atoms or a branched or cyclic alkyl group having 3 to 10C atoms or an aromatic ring system having 5 to 24C atoms;
m is 0 or 1;
n is 0 or 1;
r is 0 or 1;
s is 0 or 1;
t is 0 or 1.
13. An oligomer, polymer or dendrimer containing one or more compounds according to any one of claims 1 to 12, wherein one or more of the bonds forming the polymer, oligomer or dendrimer may be located at any desired position in formula (1).
14. A formulation comprising at least one compound according to any one of claims 1 to 12 and at least one solvent.
15. Process for the preparation of a compound according to any one of claims 1 to 12, characterized in that it comprises a C-C Suzuki coupling reaction between a spirobifluoreneboronic ester derivative and a halogenated diaminobenzene.
16. Use of a compound according to any one of claims 1 to 12 in an electronic device.
17. An electronic device comprising at least one compound according to any one of claims 1 to 12, selected from organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic dye sensitized solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells, organic laser diodes and organic plasmon light emitting devices.
18. Electronic device according to claim 17, selected from organic electroluminescent devices, characterized in that the compound according to any of claims 1 to 12 is contained as hole transport material in a hole transport or hole injection or exciton blocking or electron blocking layer or as host material for fluorescent or phosphorescent emitters in an emitting layer.
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